Synthesis of novel molecular sieves using a metal complex as a template

ABSTRACT

The synthesis and characterization of novel molecular sieves containing bis(pentamethylcyclopentadienyl) cobalt(III) ion are described. Several types of molecular sieves were prepared using the cobalt metal complex as a template that was shown to be incorporated as a guest molecule within the molecular sieve. Molecular sieves prepared using bis(pentamethylcyclopentadienyl) cobalt(III) ion as template were characterized as having a pore size at least as large as 7 Å. Other molecular sieves were also prepared using bis(cyclopentadienyl) cobalt(III) templates. The compounds are attractive as catalysts in a wide range of applications.

The United States Government has rights in the present inventionpursuant to grant CHE-9157014 awarded by the National ScienceFoundation.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates generally to synthesis of molecular sievecomplexes and more specifically to the use of certainbis(cyclopentadienyl) cobalt ion complexes as structure directing agentsor templates.

2. Description of Related Art

The incorporation of metal complexes during the synthesis of molecularsieves is known to be useful for synthesis of zeolite "ship-in-a-bottle"complexes. NaX zeolites have been synthesized around metalphthalocyanines (Balkus, et al, 1992; Balkus and Kowalak, 1992). In afew cases the metal complex may also function as a structure directingagent during crystallization. The metal complexbis(cyclopentadienyl)cobalt(III) ion, Cp₂ Co⁺, has been reported to be atemplate for isostructural ZSM-51 and Nonasil in hydroxide and fluoridemedia as well as ZSM-45 (Balkus and Shepelev, 1993A, 1993B; U.S. Pat.No. 4,568,654). Nonasil is described in U.S. Pat. No. 4,556,549 as anall-silica clathrasil type molecular sieve. The metal complex iscompletely encapsulated as indicated by the x-ray structure that showsthe largest openings to the nonasil cages are 6-membered rings (Behrensand van de Goor, 19 - - - ).

The formation of many molecular sieves depends on the presence oftemplate molecules that affect the gel chemistry and/or act as a voidfiller (R. Szostak, 1989). Most of the templates that have beenevaluated for molecular sieve synthesis are based on organic molecules,particularly aliphatic amines. By comparison, the structure directingproperties of metal complexes are relatively unexplored. Cobalticiniumion, Cp₂ Co⁺, has been shown to be a template for the clathrate typemolecular sieves Nonasil and ZSM-51 as well as ZSM-45. In the case ofZSM-51, the template claimed for its synthesis was bis(cyclopentadienyl)cobalt(III) hexafluorophosphate. More recently, Cp₂ CoOH was shown to bea template for the aluminum phosphate molecular sieves AlPO₄ -5 andAlPO₄ -16. Cp₂ Co⁺ has been reported to produce the all-silicaclathrasils octadecasil and dodecasil.

Recent work has thus indicated that the role of the metal and the effectof functionalizing the bis(cyclopentadienyl) rings may lead to new typesof molecular sieves when these agents are used as structure directingagents. However, the structure directing effects for synthesis ofmolecular sieves are largely unpredictable and not well understood. Theavailability of novel molecular sieves would be beneficial in extendingthe range of zeolite type catalysts and in semiconductor applications.

SUMMARY OF THE INVENTION

The present invention addresses problems inherent in the art byproviding novel molecular sieve compounds and processes for producingthe novel compounds. The present work shows that certain metal complexescan be employed as templates or structure-directing agents. Several newmolecular sieve compounds have been produced. The compounds aremicrocrystalline and microporous and incorporate the templating agentmetal used in the formation of the compound.

In particular, bis(cyclopentadienyl)cobalt(III) ion (Cp₂ Co⁺), has beenshown to be a template for synthesis of the aluminum phosphate molecularsieves exemplified by AlPO₄ -5 and AlPO₄ -16. This is an unexpectedfinding to the extent that this metal complex will provide a templatefor both channel (AlPO₄ -5) and cage (AlPO₄ -16) molecular sieves. TheCp₂ Co⁺ complex is relatively rigid, unlike many typical organictemplates. This provides an opportunity to evaluate the effects of size,shape and symmetry on the structure directing properties of the complexby the modifying the Cp ring(s) with different substituents.

Employing a fully methylated derivative,bis(pentamethylcyclopentadienyl) cobalt(III) ion (Cp₂ *Co⁺), theinventor has produced five new molecular sieves. It is contemplated thatother new molecular sieves can be produced by altering the template; forexample, any combination of alkyl groups on the cyclopentane ring suchas methyl, ethyl, propyl, etc. as well as various metal species such asNi²⁺, Fe²⁺, and other Group VIII metal ions. Nevertheless, theproperties of these templates would be expected to differ from the bispentamethylcyclopentadienyl species employed in the present invention.

The different metal complexes so far studied have unique structuredirecting properties, such that bis(cyclopentadienyl)cobalt(III) iondoes not promote formation of the same structures asbis(pentamethylcyclopentadienyl) cobalt(III) ion. This is likely due tothe different features of each complex, including size, shape and chargedistribution.

Overall, and in general, the invention discloses novel microcrystallinemolecular sieves prepared from template directing metallo organiccomplexes. In particular embodiments, a metal microcrystalline silicamolecular sieve with a nominal pore diameter of at least 7.2 Å isformed. Such silica molecular sieves incorporate the positively chargedmetal ion as a guest molecule. Among the unique structures producedusing the (Cp₂ *Co⁺) ion is a microcrystalline silica molecular sievecharacterized as a yellow crystalline product, UTD-1. UTD-1 was preparedas a single phase product employing bis(pentamethylcyclopentadienyl)cobalt(III) ion as template. The crystalline material was formed from agel containing sodium hydroxide, the organic metal template and fumedsilica. UTD-1 is formed from a gel with the approximate molecular ratioof water to SiO₂ of about 60, sodium ion to SiO₂ of about 0.1, hydroxylion to silica SiO₂ of about 0.2 and the bis(pentamethylcyclopentadienyl)cobalt(III) ion template ratio to SiO₂ of about 0.1. The x-raydiffraction powder patterns for the UTD-1 as synthesized and thecalcined material indicate the uniqueness of the molecular sieve. Asexpected, there is decomposition of the organic portion of the templateafter calcination at 500° C. The overall structure, however, is quitestable. The bright yellow color of UTD-1 indicates that thepentacyclodienyl metal ion complex is entrapped in the crystals as aguest molecule. The metal complex template is relatively large and isnot removed by either aqueous or organic extraction procedures. Channelsor cages within the molecular complex therefore are at least as large asthe Cp* rings that measure approximately 7.2 Å. UTD-1 is also arelatively large pore material as suggested by the low angle reflectionsobtained on x-ray crystallographic measurement.

While UTD-1 is quite stable, there is an indication of decomposition atapproximately 350° C. Calcination is accompanied by a change in colorfrom yellow to pale green. It is likely that this change of colorrepresents decomposition of the organic portion of the metal complexwith concomitant formation of metal oxide. There was no evidence offramework substitution by the cobalt during formation of the molecularsieve.

Yet another embodiment of the present invention is illustrated in theformation of the molecular sieve UTD-2. This compound also incorporatesCp*₂ Co as a guest molecule but is different in structure inincorporating aluminum and phosphorous as part of the framework. UTD-2is also obtained as a single phase product from a gel having molarratios of 1:0.9:0.4:0.86:0.025:50 for the components Al₂ O₃ :P₂ O₅ :SiO₂: (TPA)₂ O: (Cp*₂ Co)₂ O:H₂ O. Of course, these ratios may be variedsomewhat. The preferred Al₂ O₃ /SiO₂ molar ratio is 2.5, although rangesas high as 4 or as low as 1 are also suitable. Using ratios outside ofthe range 4>2.5>1 typically results in an amorphous material. Aconvenient procedure for the preparation of UTD-2 and similar molecularsieves is to prepare two mixtures; mixture 1 from aluminum hydroxide andphosphoric acid and mixture 2 from silica, preferably fumed silica, CP*₂Co⁺ hydroxide, and tetrapropylammonium hydroxide. Of course, one mayvary not only the ratios but the type of quaternary ammonium compoundemployed; for example, other tetra alkyl ammonium hydroxides. UTD-2 isconveniently formed after mixing mixture 1 and mixture 2, heating for aperiod of time at approximately 200° C. cooling, diluting and separatingthe crystalline material. UTD-2, like UTD-1, is yellow, indicatinginclusion of the metal template within the molecular sieve.

The novel compound UTD-2 may also be prepared using only Cp*₂ CoOH astemplate. The presence of tetrapropyl ammonium hydroxide, however,appears to be conducive to obtaining better yields of UTD-2. When usingonly Cp*₂ CoOH as the template, gels with molar ratios of about1:0.9:0.4:0.32:50 to Al₂ O₃ :P₂ O₅ :SiO₂ (Cp*₂ Co)₂ O:H₂ O may beemployed as preferred ratios. Variations of Al₂ O₃ /SiO₂ may be employedas previously discussed, preferably in the range of 4>2.5>1.

A new component, UTD-5, also resulted from the single template syntheticprocedure used to obtain UTD-2. The new material UTD-5 wasdistinguishable from UTD-2 in its x-ray pattern as synthesized from thegel mixture and also after calcination at 500° C. The unusual dark greencolor of the calcined UTD-5 suggested formation of cobalt oxide and/orpossibly the free metal.

Yet another embodiment of the present invention, the unsubstituted formof bis(cyclopentadienyl) cobalt(III), was used as a template to form aUTD-3/SAPO compound. The cobalt ion template was used in combinationwith tetrapropylammonium hydroxide. This compound was prepared usingprocedures analogous to those used to prepare UTD-2 except that thesecond mixture incorporated Cp₂ CoOH rather than Cp*₂ CoOH. Preferredmolar ratios for Al₂ O₃ :P₂ O₅ :SiO₂ :(TPA)₂ O:(Cp₂ Co)₂ O:H₂ O wereabout 1:0.9:0.4:0.86:0.025:48. The new UTD-3 SAPO compound was yellow incolor, microcrystalline, and like the other compounds, changed colorafter calcination at 500° C. The new compound had a unique x-ray powderdiffraction pattern. The calcined sample was a sky-blue color afterheating for several hours at 500° C. UTD-3 could also be prepared as asingle phase from the gel containing cobalt(II) ions instead of silicaand Cp₂ CoOH as the only template. This UTD-3 compound is a modificationof the UTD-3 to the extent that it is isolated as a dark blue-greenproduct; however, it is single phase and has an x-ray diffractionpattern substantially the same as UTD-3. UTD-3-CoAPO is prepared bymixing phosphoric acid, a cobalt salt, preferably cobalt sulfate, thenadding aluminum hydroxide and the bis(cyclopentadienyl) cobalt(III)hydroxide template, mixing the gel for several hours, e.g.,approximately four hours, and then heating at about 200° C. for about aday, i.e., 18 to 24 hours, to provide a single phase product. Preferredmolar ratios for Al₂ O₃ :P₂ O₅ :CoO:(Cp2Co)₂ O:H₂ O are about0.8:1:0.4:0.75:53. However, the ratios may be employed within thisgeneral range to obtain UTD-3 CoAPO.

Yet another embodiment of the present invention UTD-6 may be preparedagain employing the bis(pentamethylcyclopentadienyl) cobalt(III)template. In a particular embodiment, UTD-6 was prepared using twotemplates, the bis(cyclopentadienyl) complex and tetrabutylammoniumhydroxide. The compound was prepared from a silicoaluminum phosphategel. The preferred component molar ratios were about1:0.9:0.4:0.86:0.16:75 for Al₂ O₃ :P₂ O₅ :SiO₂ :(TBA)₂ O:H₂ O. UTD-6 wasconveniently prepared by admixing two mixtures; the first containingaluminum hydroxide and phosphoric acid; and the second containing fumedsilica and the two templates.

The five new molecular sieve compounds described above are illustrativeof the types of new compounds that may be prepared using a metal organiccomplex. For the first time, the inventors have shown the structuredirecting properties of cobalticinium ion complexes and that havedemonstrated molecular sieves can be formed without an organo cation.The present invention illustrates the general types of novel structuresthat may be produced in the presence of bis(pentamethylcyclopentadienyl)cobalt(III) ion as the template. It is possible that even larger porematerials may be produced by increasing the bulkiness of the complexcobalt(III) ion; for example, by appropriate substituent groups on thecyclopentane rings.

While the complete range of reactions and properties of the newmicrocrystalline metal molecular sieves has not been explored, it isrecognized that related compounds have been well utilized as catalysts.More specifically, such compounds have been used in catalytichydrofining, cracking, and as selective adsorbants. Many of these usesare described in more detail in U.S. Pat. No. 4,440,871 incorporatedherein by reference where it is noted that in general silicon aluminumphosphate molecular sieves are similar to zeolite catalysts in severalof their properties.

By analogy with the Cp₂ Co⁺ /nonasil complexes, the new molecular sievesare expected to exhibit special optical effects that could be exploitedin memory storage devices. Molecular sieves are increasingly beingdeveloped as sensors in semiconductor devices.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A. Powder x-ray diffraction pattern of UTD-1 as synthesized.

FIG. 1B. Powder x-ray diffraction pattern of UTD-1 after calcination(500° C., 4 hr) samples. CaF₂ was used as an internal standard.

FIG. 2. Scanning electron micrograph of UTD-1.

FIG. 3A. FT-IR spectra for UTD-1as synthesized. Sample prepared as KBrpellet.

FIG. 3B. FT-IR spectrum of UTD-1 after calcination (500° C.) Sampleprepared as KBr pellet.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The templating ability of metallocenes in the synthesis of crystallinemicroporous metal oxides is the general focus of the present invention.The inventors have prepared and characterized a series of novel silicatype molecular sieves, designated as "UTD" compounds. The novelstructures are produced in the presence ofbis(pentamethylcyclopentadienyl)cobalt(III) ion, Cp*₂ Co⁺, as thetemplate. Since the less bulky Cp₂ Co⁺ appeared to favor formation ofthe smaller pore clathrate type molecular sieves, the inventors havereasoned that addition of methyl groups to the cyclopentadienyl ringswill encourage the crystallization of larger pore materials.

It is known that the crystallization of zeolite molecular sieves in thepresence of metal chelates may result in encapsulation of the complexes(U.S. Pat. No. 5,167,942). This is a viable method for the preparationof zeolite ship-in-a-bottle complexes (Balkus and Gabrielov, 1994);however, the metal complex may also serve as a structure directingagent. The formation of many molecular sieves depends on the presence oftemplate molecules that affect the gel chemistry and/or act as a voidfiller.

Most of the templates that have been evaluated for molecular sievesynthesis are based on organic molecules, especially aliphatic amines.By comparison, the structure directing properties of metal complexes arevirtually unknown. Cobalticinium ion, Cp₂ Co⁺, has been shown to be atemplate for the clathrate type molecular sieves Nonasil and ZSM-51(Balkus and Shepelev, 1993; Balkus and Shepelev, 1993B; U.S. Pat. No.4,568,564). More recently, work in the inventors' laboratory showed thatCp₂ CoOH acts as a template for the production of AlPO₄ -16 and SAPO-16.Molecular sieves of this type had previously required an organo-cationto form and, specifically in the case of AlPO₄ -16 or SAPO-16, onlyquinuclidene was known to generate this topology.

The following examples are provided for purposes of clarification andshould not be considered as limiting. One skilled in the art wouldrecognize in light of the present disclosure that although the specifiedmaterials and conditions are important in practicing the invention,unspecified materials and conditions are not excluded as long as they donot prevent the benefits of the invention from being realized.

EXAMPLE 1

This example illustrates the preparation of an all-silica molecularsieve using a bis(pentamethylcyclopentadienyl) cobalt(III) ion as atemplate. The microcrystalline silica molecular sieve incorporates thecomplexed cobalt ion, apparently as a guest molecule.

Preparation of UTD-1

The metal complex Cp*₂ CoPF₆ was prepared according to the literatureprocedure (Kolle and Khouzami, 1981). The complex was converted to thechloride derivative over Dowex-50W cation exchange resin by firstadsorbing the Cp*₂ Co⁺ ion followed by elution with 1M HCl. The Cp*₂CoCl was then transformed to the hydroxide form over an aqueous slurryof silver oxide at 70C. The concentration of the brown Cp*₂ CoOHsolution was determined by potentiometric titration. The solution wasthen used in the molecular sieve synthesis.

UTD-1 was prepared as a single phase product by combining NaOH, a 31.6%aqueous Cp*₂ CoOH solution and fumed silica to form a gel with thefollowing molar ratios.

    ______________________________________                                               H.sub.2 O/SiO.sub.2                                                                     60                                                                  Na.sup.+ /SiO.sub.2                                                                     0.1                                                                 OH.sup.- /SiO.sub.2                                                                     0.2                                                                 Cp*.sub.2 Co.sup.+ /SiO.sub.2                                                           0.1                                                          ______________________________________                                    

The gel was aged with stirring for 1 hour and then transferred to a 23mL Teflon-lined pressure reactor (Parr). The reactor was heated at 175°C. under static conditions for 2 days. The resulting yellow crystallineproduct was washed with deionized water, suction filtered and then driedat 90° C. for 2 hours.

FIG. 1A shows the X-ray diffraction (XRD) powder pattern data for UTD-1as synthesized. FIG. 1B shows the XRD of calcined UTD-1. Although thereare changes in peak intensity after calcination at 500° C. anddecomposition of the template occurs, the structure appears quitestable. FIG. 2 shows the bundles of rectangular shaped crystals obtainedafter synthesis. These results support a single phase material. Thebright yellow color of UTD-1 indicated that the Cp*₂ Co⁺ template wasentrapped in the crystals as a guest molecule. The metal complex cannotbe removed by aqueous or organic extraction. This implied that thechannels or cages were at least as large as the Cp* rings (7.2 Å) inorder to accommodate the complexes. The low angle reflections in FIGS.1A and 1B also suggested a large pore material. Additionally,preliminary adsorption experiments using calcined UTD-1 indicated a ˜20%by weight increase upon exposure to cyclohexane (kinetic diameter 6.0Å). Pore size determination by more direct adsorption methods iscomplicated by the occluded cobalt species.

                  TABLE 1A                                                        ______________________________________                                        (UTD-1 as synthesized)                                                                     d      %                                                         ______________________________________                                         1.            14.686   48                                                     2.            11.742   44                                                     3.            8.086     6                                                     4.            7.339    23                                                     5.            6.058    53                                                     6.            5.872     8                                                     7.            6.459    50                                                     8.            4.9754   50                                                     9.            4.892    10                                                    10.            4.553    100                                                   11.            4.031    57                                                    12.            4.193    25                                                    13.            3.913    15                                                    14.            3.829     5                                                    15.            3.710     5                                                    16.            3.668    41                                                    17.            3.611    34                                                    18.            3.448     4                                                    19.            3.390    23                                                    20.            3.206     5                                                    21.            3.084    11                                                    22.            3.006    23                                                    23.            2.799     8                                                    24.            2.763    18                                                    25.            2.738     3                                                    26.            2.637     4                                                    27.            2.509     4                                                    28.            2.489     3                                                    29.            2.445     7                                                    30.            2.406     3                                                    ______________________________________                                    

                  TABLE 1B                                                        ______________________________________                                        (calcined at 500° C.)                                                          d     %                                                               ______________________________________                                                14.620                                                                              100                                                                     11.509                                                                              64                                                                      9.466 6                                                                       6.094 10                                                                      4.882 13                                                                      4.478 23                                                                      4.384 7                                                                       4.211 45                                                                      4.049 10                                                                      3.955 6                                                                       3.843 5                                                                       3.735 2                                                                       3.659 17                                                                      3.560 14                                                                      3.400 9                                                                       3.066 3                                                                       3.066 5                                                                       2.769 6                                                                       2.646 1                                                                       2.553 1                                                                       2.466 1                                                                       2.436 2                                                                       2.374 2                                                               ______________________________________                                    

There was no evidence of complex decomposition during synthesis fromspectroscopic analysis of encapsulated and free complexes. The UV-Visspectrum of a UTD-1 nujol mull was broadened and slightly red shifted(<15 nm) compared to an aqueous solution of Cp*₂ CoOH (290, 338sh, 406shnm). However, this shift to lower energy was also noted for Cp₂ Co⁺ inNonasil and AlPO₄₋ 5 molecular sieves (Balkus and Shepelev, 1993A).Thermogravimetric analysis (TG) of Cp*₂ CoPF₆ indicated the onset ofdecomposition at ˜350° C., which is significantly higher than the UTD-1synthesis temperature (175° C.). Similarly, UTD-1 begins to lose weightat ˜350° C. with a change in color from yellow to pale green. Only a 5%weight change was measured up to 900° C. The small change is consistentwith loss of the organics and probable formation of occluded oxides.

There was no evidence of framework substitution by cobalt. The FT-IRspectrum of UTD-1 also indicated the presence of intact Cp*₂ Co⁺ asevidenced by the ν_(CH) at 2915 cm⁻¹ that can be compared to the freeCp*₂ CoPF₆ complex with a C--H band at 2920 cm⁻¹. Similarly, a C--Cstretch at 1476 cm⁻¹ for the free complex appeared at 1480 cm⁻¹ inUTD-1. There were a variety of other bands that might be ascribed to theencapsulated metal complex; however, they were either masked by thebands associated with the molecular sieve or were quite weak.

FIG. 3A shows the FT-IR spectrum in the region 1500-400 cm⁻¹ for UTD-1as synthesized. FIG. 3B shows the FT-IR spectrum after calcination at500° C. There are two strong bands at 1237 and 1092 cm⁻¹ that aretypical of the asymmetric Si--O stretches observed for crystallinesilicates. There are no significant shifts for these bands aftercalcination; however, two shoulders are resolved at 1140 and 1076 cm⁻¹.The bands that appear in the symmetric stretching region (812, 787, 642cm⁻¹), as well as the more structure sensitive region (612, 582 and 537cm⁻¹), appear quite different from known silicate phases.

The results indicate that an all-silica phase UTD-1 can be synthesizedusing the metal complex Cp*₂ CoOH as a template that becomesincorporated as a guest molecule. The data indicate that UTD-1 is alarge pore material (>7 Å).

EXAMPLE 2

Another new molecular sieve was prepared as illustrated in the followingexample. This compound, like UTD-1, also incorporates the template Cp*₂Co⁺ as a guest molecule but differs in including aluminum and phosphorusas part of the framework.

Preparation of UTD-2

UTD-2 was obtained as a single phase product from a gel having molarratios Al₂ O₃ :P₂ O₅ :SiO₂ :(TPA)₂ O:(Cp*₂ Co)₂ O:H₂O--1:0.9:0.4:0.86:0.025:50. The preferred Al₂ O₃ /SiO₂ molar ratio is2.5. Taking the Al₂ O₃ /SiO₂ ratios out of the range 4>2.5>1 may resultin an amorphous material. The procedure involves first preparing twomixtures as follows.

Mixture 1 was prepared by slowly adding 2 g of aluminum hydroxide(Pfaltz & Bauer, LOT 039789, 83.34 wt %) to a solution of 2.22 g 85 wt %H₃ PO₄ (Fisher) and 2.0 g of deionized water with magnetic stirring.After adding about 1.3 g of the hydroxide, the gel became extremelyviscous and was stirred with a Teflon rod for 1 hour.

Mixture 2 was prepared by adding 0.256 g fumed silica (0.007μ, Aldrich)to a mixture of 0.58 g of a 30 wt % Cp*₂ CoOH solution in water and 9.28g of 40 wt % tetrapropylammonium hydroxide (TPAOH obtained from Alfa).Mixture 2 was not viscous and easily obtained homogeneity.

Mixture 2 was added slowly to mixture 1 and the final mixture wasstirred for approximately 6 hours in order to achieve a homogeneous gel.The gel was transferred into a 25 cm³ Teflon-lined pressure reactor(Parr) that was subsequently placed in an oven having a constanttemperature of 200° C. After 20 hrs heating at autogenous pressure, themixture was cooled to room temperature and diluted with 100 mL ofdeionized water. The bright yellow crystals were separated from a whiteamorphous material by centrifugation and/or sedimentation, washed withdeionized water and isolated by filtering through a nitrocellulosemembrane (2 μm) under suction. The solid yellow residue was dried atroom temperature for 24 hrs. UTD-2 appeared on SEM images as a singlephase.

                  TABLE 2                                                         ______________________________________                                        X-ray pattern for UTD-2 as synthesized                                        #       2 theta      d, A    (rel. int., %)                                   ______________________________________                                        1.      6.270        14.085  (100)                                            2.      11.307       7.819    (4)                                             3.      11.720       7.545    (3)                                             4.      12.542       7.052    (9)                                             5.      18.844       4.705   (27)                                             6.      19.272       4.602   (50)                                             7.      20.267       4.378   (23)                                             8.      23.014       3.861    (2)                                             9.      25.215       3.529   (61)                                             10.     27.062       3.292    (6)                                             11.     31.903       2.803    (3)                                             12.     33.695       2.658   (12)                                             13.     34.283       3.393    (7)                                             14.     36.014       2.492    (1)                                             15.     38.165       2.356    (1)                                             ______________________________________                                    

EXAMPLE 3

UTD-2 could be also obtained using only Cp*₂ CoOH as template, as shownin the following example.

Single Template Synthesis of UTD-2

The single template synthesis of UTD-2 was substantially the same asthat described in Example 2 except that mixture 2 was prepared by adding0.256 g fumed silica to 7.76 g of a 30 wt % Cp*₂ CoOH solution in water.The final gel had molar ratios Al₂ O₃ :P₂ O₅ : SiO₂ :(Cp*₂ Co)₂ O:H₂O=1:0.9:0.4:0.32:50. The x-ray pattern of the yellow sample obtainedafter crystallization and purification indicated the presence of UTD-2(about 30%) and a second component, UTD-5. Most of the peaks of UTD-5are broad. UTD-5 was isolated by sedimentation and/or centrifugation ofthe more dense layer.

                  TABLE 3                                                         ______________________________________                                        X-ray Pattern for UTD-5 as Synthesized                                        #       2 theta      d, A    (rel. int., %)                                   ______________________________________                                        1       6.51         13.57   (24)                                             2       10.89        8.12    (16)                                             3       12.31        7.18    (21)                                             4       12.92        6.85    (31)                                             5       13.12        6.740   (30)                                             6       16.78        5.28    (55)                                             7       20.88        4.25    (100)                                            8       22.12        4.02    (71)                                             9       23.13        3.84    (25)                                             10      26.51        3.36    (24)                                             11      29.21        3.06    (31)                                             12      32.07        2.79    (20)                                             ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        X-ray pattern for UTD-5 calcined at 500° C. (dark green)               #       2 theta      d, A    (rel. int., %)                                   ______________________________________                                        1       6.48         13.63   (92)                                             2       7.52         11.75   (46)                                             3       12.45        7.10    (42)                                             4       21.04        4.22    (96)                                             5       21.30        4.17    (100)                                            6       22.30        3.98    (62)                                             7       24.48        3.63    (33)                                             ______________________________________                                    

EXAMPLE 4

This example illustrates the formation of a novel microcrystallinemolecule sieve using bis(cyclopentadienyl) cobalt(III) ion as thetemplate.

Preparation of UTD-3-SAPO

Mixture 1 was prepared as described in Example 2. Bis (cyclopentadienyl)cobalt (III) hydroxide (Cp₂ CoOH) was used as a template in combinationwith tetrapropylammonium hydroxide (TPAOH).

Mixture 2 was prepared by adding 0.256 g fumed silica to a mixture of0.354 g of a 31 wt % Cp₂ CoOH solution in water and 9.28 g of 40 wt %tetrapropylammonium hydroxide. The molar ratios were as follows: Al₂ O₃:P₂ O₅ :SiO₂ :(TPA)₂ O:(Cp₂ Co)₂ O:H₂ O=1:0.9:0.4:0.86:0.025:48. Thecrystallization and purification procedures were similar to thosedescribed in Example 2. The top and bottom layers (white material) wereseparated from the intermediate bright yellow fraction by sedimentationand/or centrifugation. The yellow fraction was isolated as UTD-3. Theyellow sample turned sky-blue after calcination at 500° C. X-ray powderdiffraction patterns for UTD-3 are shown in Table 5 for the synthesizedcompound and in Table 6 after calcination.

                  TABLE 5                                                         ______________________________________                                        X-ray pattern for UTD-3 as synthesized (yellow)                               #       2 theta      d, A    (rel. int., %)                                   ______________________________________                                        1       8.588        10.288   (3)                                             2       10.898       8.112    (5)                                             3       15.936       5.557   (11)                                             4       17.279       5.128   (80)                                             5       17.694       5.009   (14)                                             6       20.805       4.266   (23)                                             7       21.919       4.052   (100)                                            8       23.278       3.818   (37)                                             9       24.790       3.589    (4)                                             10      26.938       3.307    (6)                                             11      28.226       3.159   (20)                                             12      31.313       2.854    (4)                                             13      32.171       2.780   (24)                                             14      34.202       2.620   (14)                                             15      34.956       2.565    (8)                                             16      35.881       2.507    (5)                                             ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        X-ray pattern for UTD-3 calcined 550° C. (blue color)                  #       2 theta      d, A    (rel. int., %)                                   ______________________________________                                        1       8.639        10.227  (15)                                             2       10.926       8.091   (49)                                             3       13.466       6.570   (51)                                             4       15.903       5.568   (15)                                             5       17.292       5.124   (78)                                             6       17.642       5.023   (13)                                             7       20.832       4.261   (44)                                             8       21.946       5.254   (100)                                            9       23.279       3.818   (31)                                             10      24.885       3.575   (13)                                             11      26.991       3.301   (15)                                             12      28.226       3.159   (20)                                             13      29.316       3.044   (11)                                             14      32.229       2.775   (24)                                             15      32.375       2.763   (25)                                             16      34.264       2.615   (13)                                             17      37.714       2.383   (11)                                             ______________________________________                                    

EXAMPLE 5

UTD-3 can be prepared as a single phase from the gel containing Co²⁺ions instead of silica and Cp₂ CoOH as the only template.

Synthesis of UTD-3-CoAPO

3.4 g H₂ O and 3.10 g 85% H₃ PO₄ were mixed with 1.5 g CoSO₄ 7H₂ O andstirred for thirty minutes. 2.0 g Al(OH)₃ (83.34%) was slowly added tothe solution and mixed for 1 hr. Then, 13.4 g of a 26.6% Cp₂ CoOHsolution was added to the mixture. The molar ratios were Al₂ O₃ :P₂ O₅:CoO:(Cp₂ Co)₂ O:H₂ O=0.8:1:0.4:0.75:53. The gel was mixed for 4 hrs,and then placed in an oven at 200° C. for 19 hours. The dark blue-greenproduct was a pure single phase. The x-ray pattern was similar to thatof UTD-3 shown in Table 5.

EXAMPLE 6

The compound described in the following example was prepared using twotemplates, one of which was Cp*₂ CoOH.

Preparation of UTD-6

UTD-6 was prepared from silicoaluminum phosphate gel using a Cp*₂ CoOHand tetrabutylammonium hydroxide (TBAOH) as templates. The molar ratioswere Al₂ O₃ :P₂ O₅ :SiO₂ :(TBA)₂ O:H₂ O=1:0.9:0.4:0.86:0.16:75.

Mixture 1 was prepared by slow addition of 2 g of aluminum hydroxide(Pfaltz & Bauer, LOT 039789, 83.34 wt %) to a solution of 2.22 g 85 wt %H₃ PO₄ (Fisher) and 2.0 g of deionized water with magnetic stirring.After addition of about 1.3 g of the hydroxide, the gel became extremelyviscous and was stirred with a Teflon rod for 1 hour.

Mixture 2 was prepared by adding 0.256 g fumed silica (0.007 m, Aldrich)to a mixture of 4.34 g of a 26.6 wt % Cp*₂ CoOH solution in water and11.92 g of 40 wt % TBAOH (obtained from Alfa). Mixture 2 was not viscousand easily obtained homogeneity.

Mixture 2 was added slowly to mixture 1 and the final mixture wasstirred for approximately 6 hrs in order to achieve a homogeneous gel.The gel was transferred into a 25 cm³ Teflon-lined pressure reactor(Parr) that was subsequently placed in an oven having a constanttemperature of 200° C. After 20 hours heating at autogeneous pressure,the mixture was cooled to room temperature and diluted with 100 mL ofdeionized water. The yellow product was isolated by filtration andwashed with copious amounts of water.

                  TABLE 7                                                         ______________________________________                                        X-ray pattern for UTD-6 as synthesized                                        #       2 theta      d, A    (rel. int., %)                                   ______________________________________                                        1       5.35         16.49   (100)                                            2       6.44         13.72   (61)                                             3       11.90        7.43    (21)                                             4       17.49        5.07    (71)                                             5       19.77        4.49    (43)                                             6       29.03        3.07    (50)                                             7       30.91        2.89    (25)                                             8       35.30        2.54    (32)                                             9       35.74        2.51    (21)                                             10      35.81        2.50    (21)                                             ______________________________________                                    

REFERENCES

The following references to the extent that they provide exemplaryprocedural or other details supplementary to those set forth herein arespecifically incorporated herein by reference.

K. J. Balkus, Jr. and S. Kowalak, U.S. Pat. No. 5,167,942, 1992.

K. J. Balkus, Jr. and S. Shepelev, Micropor. Mater., 1993A, 1, 383.

K. J. Balkus, Jr. and S. Shepelev, Petrol. Preprints, 1993B, 38, 512.

E. W. Valyecsik, U.S. Pat. No. 4,568,654, 1986.

Valyecsik, E. W., U.S. Pat. No. 4,556,549 (Dec. 3, 1985).

U. Kolle and F. Khouzami, Chem. Ber., 1981, 114, 2929.

Balkus, K. J., Jr., Hargis, C. D. and Kowalak, S., ACS Symp. Ser. 49,348 (1992).

Szostak, R. in Molecular Sieves, Van Nostrand, New York, N.Y. p. 79, 84,1989.

What is claimed is:
 1. A metal microcrystalline silica molecular sievehaving a nominal pore diameter greater than about 7.2 Å thatincorporates a cobalticinium ion as a guest molecule and that assynthesized has an X-ray powder diffraction pattern that includes atleast the lines as set forth in Table 1A.
 2. The metal microcrystallinesilica molecular sieve of claim 1 that is prepared from a gel having themolar ratios:(a) about 60 for H₂ O/SiO₂ ; (b) about 0.1 for Na⁺ /SiO₂ ;(c) about 0.2 for OH⁻ /SiO₂ ; (d) about 0.1 for Cp₂ Co⁺ /SiO₂ whereinCp₂ Co⁺ is bis (pentamethylcyclopentadienyl)Cobalt III ion.
 3. A metalmicrocrystalline silica molecular sieve that after calcination has atleast an x-ray powder diffraction pattern that includes at least thelines as set forth in Table 1B.
 4. A microcrystalline silicoaluminumphosphate molecular sieve that incorporates a cobalticinium ion as aguest molecule and has an X-ray powder diffraction pattern that includesat least the lines set forth in Table
 7. 5. The microcrystallinesilicoaluminum phosphate molecular sieve of claim 4 wherein themolecular sieve has the composition Al₂ O₃ :P₂ O₅ :SiO₂ : (TBA)₂ O: (Cp₂Co)₂ O:H₂ O in the molar ratio of 1:0.9:0.4:0.86:0.16:75 where TBA istetrabutylammonium ion and Cp₂ Co is bis(pentamethylcyclopentadienyl)cobalt(III) ion.